CN110240797A - 3D printing composition and its preparation method and application - Google Patents
3D printing composition and its preparation method and application Download PDFInfo
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- CN110240797A CN110240797A CN201810198179.4A CN201810198179A CN110240797A CN 110240797 A CN110240797 A CN 110240797A CN 201810198179 A CN201810198179 A CN 201810198179A CN 110240797 A CN110240797 A CN 110240797A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/10—Peculiar tacticity
- C08L2207/14—Amorphous or atactic polypropylene
Abstract
The present invention relates to polymeric material fields, disclose a kind of 3D printing composition, the composition contains thermoplastic polyurethane, polyolefin, polyolefin elastomer, compatilizer, inorganic filler and antioxidant, on the basis of the total weight of the composition, the content of the thermoplastic polyurethane is 50-95 weight %, the content of the polyolefin is 1-20 weight %, the content of the polyolefin elastomer is 1-20 weight %, the content of the compatilizer is 1-20 weight %, the content of the inorganic filler is 0.1-2 weight %, the content of the antioxidant is 0.05-1 weight %.The advantages that 3D printing material of the invention has both high resiliency, high intensity, high tenacity, high-dimensional stability, nontoxic safety and environmental protection is suitable for a variety of fusion sediment methods and prints type, have broad application prospects in 3D printing technique.
Description
Technical field
The present invention relates to polymeric material fields, and in particular, to a kind of 3D printing composition and preparation method thereof and answers
With.
Background technique
3D printing, also known as increasing material manufacturing are one kind of rapid shaping technique.Its principle is to first pass through computer modeling or sweep
Prototype is retouched, digital model is obtained, then threedimensional model is resolved into the two-dimensional section data of multilayer, then pass through software and numerical control
System is successively printed material, ultimately forms 3D solid.As the core technology for pushing tertiary industry revolution, 3D printing
Have the characteristics that networking, digitlization, personalization, defense military, aerospace, industry pattern design, product prototype design,
The fields such as biologic medical have a wide range of applications.The mainstream forming method of 3D printing includes melting deposition modeling
(FusedDeposition Modeling, FDM), stereolithography apparatus (Stereo Lithography Apparatus,
SLA), selective laser sintering (Selective Laser Sintering, SLS) etc..
3D printing product needs not move through injection molding, can be obtained intensity height, the forming part of good toughness.It can be directly used for
The inspection of intensity, performance is carried out to model, verifies reasonability, the feasibility of manufacturing process, the beauty of moulding of product design structure
The property seen, can time update, improve product design, to meet the needs in market, to greatly shorten the development cycle of new product,
Development cost is reduced, enterprise is made to have stronger competitiveness.
Wherein 3D printing high resiliency consumptive material can be used in various fields, for example, clothes, shoes, mother and baby's articles, sporting goods,
Tableware, toy etc..Have elastomeric macromolecule 3D printing consumptive material mainly using thermoplastic polyurethane as raw material in the prior art,
And intensity, toughness and dimensional stability are poor.
Summary of the invention
The purpose of the invention is to overcome drawbacks described above of the existing technology, providing a kind of has high resiliency, high-strength
Degree, high tenacity, the 3D printing consumptive material composition preparation method of high-dimensional stability and application.
To achieve the goals above, in a first aspect, the present invention provides a kind of 3D printing composition, the composition contains thermoplastic
Property polyurethane, polyolefin, polyolefin elastomer, compatilizer, inorganic filler and antioxidant, using the total weight of the composition as base
Standard, the content of the thermoplastic polyurethane is 50-95 weight %, the content of the polyolefin is 1-20 weight %, the polyene
The content of olefin elastomer is 1-20 weight %, the content of the compatilizer is 1-20 weight %, the content of the inorganic filler is
0.1-2 weight %, the antioxidant content be 0.05-1 weight %.
Second aspect, the present invention provides a kind of preparation methods of 3D printing material, this method comprises: by above-mentioned composition
It successively mixes, be granulated and form.
The third aspect, the present invention provides 3D printing materials made from the above method.
Fourth aspect, the present invention provides the application of above-mentioned composition or printed material in fusion sediment method 3D printing.
Compared with prior art, technical solution of the present invention has the advantage that
It is nontoxic that 3D printing material of the invention has both high resiliency, high intensity, high tenacity, high-dimensional stability, safety and environmental protection
The advantages that, it is suitable for a variety of fusion sediment methods and prints type, has broad application prospects in 3D printing technique.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Fig. 1 is with the slippers of the 3D printing file printing of embodiment 1.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
In a first aspect, the present invention provides a kind of 3D printing composition, the composition contain thermoplastic polyurethane, polyolefin,
Polyolefin elastomer, compatilizer, inorganic filler and antioxidant, on the basis of the total weight of the composition, the thermoplastic poly
The content of urethane is 50-95 weight %, the content of the polyolefin is 1-20 weight %, the content of the polyolefin elastomer is
1-20 weight %, the compatilizer content be 1-20 weight %, the content of the inorganic filler is 0.1-2 weight %, described
The content of antioxidant is 0.05-1 weight %.
In 3D printing composition of the invention, under preferable case, the thermoplastic polyurethane is polyester-type and/or polyethers
Type.It is highly preferred that the thermoplastic polyurethane is more preferably polyester-type.
In 3D printing composition of the invention, on the basis of the total weight of the composition, the thermoplastic polyurethane
Content be specifically as follows 50 weight %, 55 weight %, 60 weight %, 65 weight %, 70 weight %, 73 weight %, 77 weight %,
What any two in 80 weight %, 83 weight %, 86 weight %, 90 weight %, 95 weight % and these point values were constituted
Arbitrary value in range.It is highly preferred that the content of the thermoplastic polyurethane is 70-90 weight %, further preferably 77-86
Weight %.
When the thermoplastic polyurethane component and dosage within the above range, 3D printing material can be made to have better
High resiliency, high intensity, high tenacity, high-dimensional stability and other effects.
Heretofore described polyolefin should be understood as such copolymer, by ethylene, propylene, 1- butylene, 1- amylene, 1-
The alpha-olefins such as hexene be polymerized alone or combined polymerization obtained from one kind thermoplastic resin general name, usual shore hardness D be 46-
85。
In 3D printing composition of the invention, under preferable case, the polyolefin is atactic copolymerized polypropene, block is total
At least one of poly- polypropylene, homopolypropylene and polyethylene.It is highly preferred that the polyolefin be atactic copolymerized polypropene,
At least one of block copolymerization polypropylene, homopolypropylene, further preferably atactic copolymerized polypropene and/or block copolymerization
Polypropylene is still more preferably block copolymerization polypropylene.
In 3D printing composition of the invention, on the basis of the total weight of the composition, the polyolefin contains measurer
Body can for 1% weight %, 2 weight %, 3 weight %, 5 weight %, 8 weight %, 10 weight %, 12 weight %, 15 weight %,
The arbitrary value in range that any two in 20 weight % and these point values are constituted.It is highly preferred that the polyolefin
Content is 2-15 weight %, further preferably 5-10 weight %.
In the present invention, the melt mass flow rate of the polyolefin selects there is no particular limitation can be normal for this field
Rule selection.Under preferable case, in 3D printing composition of the invention, the melt mass flow rate of the polyolefin is 1-
100g/10min.It is highly preferred that the melt mass flow rate of the polyolefin is 10-50g/10min, further preferably
20-30g/10min。
When the polyolefin component, dosage and melt mass flow rate within the above range, 3D printing material can be made
Material has better high resiliency, high intensity, high tenacity, high-dimensional stability and other effects.
Heretofore described polyolefin elastomer is a kind of High performance polyolefin, at normal temperature at caoutchouc elasticity, is had close
The features such as small, bending is big, low-temperature impact resistance is high is spent, usual shore hardness is 10-45D.
In 3D printing composition of the invention, under preferable case, the polyolefin elastomer be based elastomers and/
Or propylene-based elastomeric, it specifically, such as can be ethylene-butylene elastomer, polyethylene-hexene elastomer, ethylene-octene elasticity
At least one of body, propene-1-butene elastomer, butene-hexene elastomer and propylene-octene elastomer.It is highly preferred that described
Polyolefin elastomer is butene-hexene elastomer and/or propylene-octene elastomer, further preferably propylene-octene elasticity
Body.
In 3D printing composition of the invention, on the basis of the total weight of the composition, the polyolefin elastomer
Content is specifically as follows 1% weight %, 2 weight %, 3 weight %, 5 weight %, 8 weight %, 10 weight %, 12 weight %, 15
The arbitrary value in range that any two in weight %, 20 weight % and these point values are constituted.It is highly preferred that described poly-
The content of olefin elastomer is 2-15 weight %, further preferably 5-10 weight %.
In the present invention, it can be this field that the selection of the shore hardness of the polyolefin elastomer, there is no particular limitation
Conventional selection.Under preferable case, in 3D printing composition of the invention, the shore hardness of polyolefin elastomer is 10-45D.
It is highly preferred that the shore hardness of the polyolefin elastomer is 15-40D, further preferably 20-35D.
When the polyolefin elastomer component, dosage and shore hardness within the above range, 3D printing material can be made
With better high resiliency, high intensity, high tenacity, high-dimensional stability and other effects.
In the present invention, it can be this field conventional selection that the component selection of the compatilizer, there is no particular limitation.It is excellent
In the case of choosing, in 3D printing composition of the invention, the compatilizer is the graft of polyolefin elastomer, including maleic acid
Acid anhydride, glycidyl methacrylate, acrylate specifically, such as can be ethylene-octene copolymer grafted maleic
Acid anhydride, ethylene-octene copolymer graft glycidyl methacrylate, propylene-octene Copolymer grafted maleic anhydride and propylene-
At least one of octene copolymer graft glycidyl methacrylate.It is highly preferred that the compatilizer is propylene-octene
Copolymer grafted glycidyl methacrylate.
In the present invention, under preferable case, the grafting rate of compatilizer is 0-1 weight %, more preferably 0.5-1 weight %, from
And it can be improved the resistance to warping of 3D printing material.Wherein, grafting rate=[grafted monomers quality/(grafted monomers quality
+ grafted monomers homopolymerization amount of substance)] × 100%.Grafted monomers homopolymerization amount of substance refers to non-grafted monomer mass.With ethylene-
For octene copolymer grafted maleic anhydride, grafting rate refers to that the ethylene-octene copolymer quality being grafted is pungent divided by ethylene-
The gross mass of alkene monomer, and the gross mass of ethylene-octene monomer is equal to the quality with non-grafted ethylene-octene being grafted
With.
In the present invention, it can be this field conventional selection that the selection of the dosage of the compatilizer, there is no particular limitation.?
In 3D printing composition of the invention, on the basis of the total weight of the composition, the content of the compatilizer specifically can be
1% weight %, 2 weight %, 3 weight %, 5 weight %, 7 weight %, 9 weight %, 10 weight %, 12 weight %, 15 weight %,
The arbitrary value in range that any two in 20 weight % and these point values are constituted.It is highly preferred that the compatilizer
Content is 2-10 weight %, further preferably 3-9 weight %.
When the component of the compatilizer, grafting rate and dosage within the above range, 3D printing material can be made to have more preferable
High resiliency, high intensity, high tenacity, high-dimensional stability and resistance to warping and other effects.
In the present invention, it can be this field conventional selection that the component of the inorganic filler, there is no particular limitation.It is preferred that
In the case of, in 3D printing composition of the invention, the inorganic filler is silica, titanium dioxide, glass microballoon, talcum
At least one of powder, barium sulfate, montmorillonite and silicon powder.It is highly preferred that the inorganic filler be silica, titanium dioxide and
At least one of glass microballoon.Wherein, the silicon powder can be super-fine silicon micro-powder.
In a kind of preferred embodiment of the present invention, the inorganic filler is the mixture of titanium dioxide and silica, and
The weight ratio of the two is 1:1-2.
In the present invention, it can be this field conventional selection that the dosage of the inorganic filler, there is no particular limitation.At this
In the 3D printing composition of invention, on the basis of the total weight of the composition, the content of the inorganic filler is specifically as follows 0.1
Weight %, 0.2 weight %, 0.3 weight %, 0.4 weight %, 0.5 weight %, 0.6 weight %, 0.8 weight %, 1 weight %,
In the range that any two in 1.2 weight %, 1.5 weight %, 1.8 weight %, 2 weight % and these point values are constituted
Arbitrary value.It is highly preferred that the content of the inorganic filler is 0.2-1 weight %, further preferably 0.3-0.6 weight %.
In the present invention, it can be this field conventional selection that the average grain diameter of the inorganic filler, there is no particular limitation.
Under preferable case, in 3D printing composition of the invention, the average grain diameter of the inorganic filler is 500-5000 mesh, specifically
Ground, for example, can for 500 mesh, 800 mesh, 1000 mesh, 1300 mesh, 1500 mesh, 1800 mesh, 2000 mesh, 2500 mesh, 3000 mesh,
The arbitrary value in range that any two in 3500 mesh, 4000 mesh, 4500 mesh, 5000 mesh and these point values are constituted.More
Preferably, the average grain diameter of the inorganic filler is 800-2000 mesh.
When the inorganic filler component, dosage and average grain diameter within the above range, 3D printing material can be made to have
Better high resiliency, high intensity, high tenacity, high-dimensional stability and other effects.
In the present invention, it can be this field conventional selection that the component selection of the antioxidant, there is no particular limitation.
Under preferable case, in 3D printing composition of the invention, antioxidant can be four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester (also known as antioxidant 1010), three [2,4- di-tert-butyl-phenyl] phosphite ester (also known as antioxygens
Agent 168) and β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid n-octadecyl alcohol ester (also known as antioxidant 1076) at least
It is a kind of.It is highly preferred that the antioxidant is antioxidant 1010, at least one of antioxidant 168.Further preferably
Ground, the antioxidant are the mixture of antioxidant 1010 and irgasfos 168, and the weight ratio of the two is 1:1-2.
In the present invention, it can be this field conventional selection that the selection of the dosage of the antioxidant, there is no particular limitation.
In 3D printing composition of the invention, on the basis of the total weight of the composition, the oxidation preventive content specifically can be with
For 0.05 weight %, 0.1 weight %, 0.2 weight %, 0.4 weight %, 0.5 weight %, 0.6 weight %, 0.8 weight %, 1 weight
Measure the arbitrary value in the range that any two in % and these point values are constituted.It is highly preferred that the antioxidant contains
Amount is 0.1-0.8 weight %, further preferably 0.2-0.5 weight %.
When the antioxidant component and dosage within the above range, can make 3D printing material have preferably it is high-elastic
Property, high intensity, high tenacity, high-dimensional stability and other effects.
It is excellent in order to make 3D printing material that there is better high resiliency, high intensity, high tenacity, high-dimensional stability and other effects
In the case of choosing, the 3D printing composition, on the basis of the total weight of the composition, the content of the thermoplastic polyurethane is
70-90 weight %, the polyolefin content be 2-15 weight %, the content of the polyolefin elastomer is 2-15 weight %,
The content of the compatilizer is 2-10 weight %, and the content of the inorganic filler is 0.2-1%, and the content of the antioxidant is
0.1-0.8 weight %.
It is further preferred that the 3D printing composition, on the basis of the total weight of the composition, the thermoplastic poly
The content of urethane is 77-86 weight %, the content of the polyolefin is 5-10 weight %, the content of the polyolefin elastomer is
5-10 weight %, the content of the compatilizer are 3-9 weight %, and the content of the inorganic filler is 0.3-0.6%, the antioxygen
The content of agent is 0.2-0.5 weight %.
Second aspect, the present invention provides a kind of preparation methods of 3D printing material, this method comprises: by above-mentioned 3D printing
Composition is successively mixed, is granulated and formed.
In method of the invention, the equipment being used in mixed way can be high-speed mixer, and the mixed time is not special
Restriction, as long as be made above-mentioned composition each component be uniformly mixed.
In method of the invention, it is granulated the selection of equipment that uses to described there is no particular limitation, can be this field
Middle conventional selection, such as can be double screw extruder.Under preferable case, the draw ratio of double screw extruder can be 30:
1-53: 1, the revolving speed of double screw extruder can be 200-400rpm.
In method of the invention, to the selection of the condition of the granulation, there is no particular limitation, can be conventional in this field
Selection.Under preferable case, the condition for being granulated extrusion may include: that extrusion temperature is 190-240 DEG C, preferably 200-
230℃.Extrusion temperature in the present invention refers to that the temperature in double screw extruder controls in above-mentioned preferred scope, that is,
It says, temperature when composition passes through double screw extruder can gradually rise, but its maximum temperature is not higher than 240 DEG C, lowest temperature
Degree is not less than 190 DEG C.
In method of the invention, forms the selection of equipment that uses to described there is no particular limitation, can be this field
Middle conventional selection, such as can be 3D twine machine.
In method of the invention, to the molding condition selection, there is no particular limitation, can be conventional in this field
Selection.Under preferable case, the molding condition may include: that extrusion temperature is 230 DEG C, and extruded velocity 50r/min is led
Silk speed is 100r/min.
The third aspect, the present invention provides 3D printing materials made from the above method.
In method of the invention, it can be ability that the selection of the specification of the 3D printing material, there is no particular limitation
Conventional selection in domain.Under preferable case, the specification of 3D printing material produced by the present invention can be diameter 1.7-1.8mm.
Fourth aspect, the present invention provides above-mentioned 3D printing composition or 3D printing material in fusion sediment method in 3D printing
In application.Such as it can be melted to heat the 3D printing material of Filamentous (diameter about 1.75mm) by spray head, head of the nozzle
With minute nozzle (diameter is generally 0.2-0.6mm), is squeezed and gushed out with certain pressure for material；Spray head is along level side simultaneously
To movement, and workbench moves along the vertical direction.For the material squeezed out in this way together with previous level clinkering, a level is heavy
After the completion of product, workbench is declined the thickness of a layer by scheduled increment, is further continued for fusion sediment, is made until completing entire entity
Type.
Below will by embodiment and comparative example, the present invention will be described in detail, but be not intended to limit the present invention.With
In lower embodiment and comparative example, unless otherwise instructed, used material can be commercially available.
Thermoplastic polyurethane is purchased from Yantai Wanhua company, the trade mark 1195, and major parameter shore hardness is 35D.
Block copolymerization polypropylene is purchased from Yanshan Petrochemical company, trade mark PPH7726, major parameter melt mass flow rate
For 26g/10min.
Atactic copolymerized polypropene is purchased from Yanshan Petrochemical company, trade mark PP4925, major parameter melt mass flow rate
For 25g/10min.
Polyethylene is purchased from Yanshan Petrochemical company, trade mark YG240F, and major parameter melt mass flow rate is 24g/
10min。
Propylene-based elastomeric is purchased from Exxonmobil company, the trade mark 6202, and major parameter shore hardness is 32D.
Based elastomers are purchased from E.I.Du Pont Company, the trade mark 8200, and major parameter shore hardness is 30D.
Propylene-octene Copolymer graft glycidyl methacrylate is purchased from Jiangsu Zhi Sheng company, trade mark SOG-
02, major parameter is that grafting rate is 0.8%.
Antioxidant 1010 is purchased from Shijiazhuang Jia Tuo Chemical Industry Science Co., Ltd, the trade mark 1010.
Irgasfos 168 is purchased from Shijiazhuang Jia Tuo Chemical Industry Science Co., Ltd, the trade mark 168.
Inorganic filler silica is purchased from Qingdao Niu Senke new material, trade mark VN3.
Inorganic filler titanium dioxide is purchased from Shanghai Ming Bo new material Co., Ltd, trade mark MH.
Embodiment 1
The present embodiment is for illustrating 3D printing composition and 3D printing material and its preparation method and application of the invention.
(1) 3D printing composition is put into high-speed mixer and mixes 10min, be uniformly mixed, obtain mixture；Wherein,
The raw material of 3D printing composition forms are as follows: 800g polyester-type thermoplastic polyurethane, 90g block copolymerization polypropylene, 60g propylene-pungent
Alkene elastomer, 43g propylene-octene Copolymer graft glycidyl methacrylate (POE-g-GMA), 2g titanium dioxide are (average
Partial size is 1000 mesh), 2g silica (average grain diameter is 1000 mesh), 3g compound antioxidant (resist by 1g antioxidant 1010 and 2g
Oxygen agent 168 forms).
(2) mixture obtained in step (1) is added twin-screw extrude, coupled extrusion, obtains high resiliency modeling
Expect grain, the process conditions of double screw extruder are as follows: extrusion temperature is 200-230 DEG C, and the draw ratio of double screw extruder is 30:1,
The revolving speed of double screw extruder is 200rpm；
(3) 3D twine machine is added in elastomer grain obtained in step (2), linear 3D printing material is prepared；
(4) 3D printing material is made to the product of shape as shown in Figure 1 using fusion sediment method.Specific method are as follows: will
The 3D printing material of Filamentous (diameter about 1.75mm) is heated by spray head to be melted, and (diameter is general with minute nozzle for head of the nozzle
For 0.3mm), is squeezed and gushed out with certain pressure for material；Spray head moves in the horizontal direction simultaneously, and workbench is along the vertical direction
It is mobile.The material squeezed out in this way is together with previous level clinkering, and after the completion of a level deposition, workbench presses scheduled increasing
The thickness of amount one layer of decline, is further continued for fusion sediment, until completing entire solid modelling.
Embodiment 2
3D printing material is prepared according to the method for embodiment 1, unlike, the group of the 3D printing composition in step (1)
Become: 770g polyester-type thermoplastic polyurethane, 100g block copolymerization polypropylene, 50g propylene-octene elastomer, 90g propylene-pungent
Alkene copolymer graft glycidyl methacrylate (POE-g-GMA), 2g titanium dioxide (average grain diameter is 1000 mesh), 2g dioxy
SiClx (average grain diameter is 1000 mesh), 3g compound antioxidant (being made of 1g antioxidant 1010 and 2g irgasfos 168).
Embodiment 3
3D printing material is prepared according to the method for embodiment 1, unlike, the group of the 3D printing composition in step (1)
Become: 860g polyester-type thermoplastic polyurethane, 50g block copolymerization polypropylene, 53g propylene-octene elastomer, 30g propylene-octene
Copolymer grafted glycidyl methacrylate (POE-g-GMA), 2g titanium dioxide (average grain diameter is 1000 mesh), 2g titanium dioxide
Silicon (average grain diameter is 1000 mesh), 3g compound antioxidant (being made of 1g antioxidant 1010 and 2g irgasfos 168).
Embodiment 4
3D printing material is prepared according to the method for embodiment 1, unlike, the composition of 3D printing composition in step (1)
Are as follows: 700g polyester-type thermoplastic polyurethane, 130g block copolymerization polypropylene, 120g propylene-octene elastomer, 43g propylene-octene
Copolymer grafted glycidyl methacrylate (POE-g-GMA), 2g titanium dioxide (average grain diameter is 1000 mesh), 2g titanium dioxide
Silicon (average grain diameter is 1000 mesh), 3g compound antioxidant (being made of 1g antioxidant 1010 and 2g irgasfos 168).
Embodiment 5
3D printing material is prepared according to the method for embodiment 1, unlike, the composition of 3D printing composition in step (1)
Are as follows: 900g polyester-type thermoplastic polyurethane, 20g block copolymerization polypropylene, 30g propylene-octene elastomer, 43g propylene-octene are total
Polymers graft glycidyl methacrylate (POE-g-GMA), 2g titanium dioxide (average grain diameter is 1000 mesh), 2g silica
(average grain diameter is 1000 mesh), 3g compound antioxidant (being made of 1g antioxidant 1010 and 2g irgasfos 168).
Embodiment 6
3D printing material is prepared according to the method for embodiment 1, unlike, the composition of 3D printing composition in step (1)
Are as follows: 500g polyester-type thermoplastic polyurethane, 200g block copolymerization polypropylene, 200g propylene-octene elastomer, 93g propylene-octene
Copolymer grafted glycidyl methacrylate (POE-g-GMA), 2g titanium dioxide (average grain diameter is 1000 mesh), 2g titanium dioxide
Silicon (average grain diameter is 1000 mesh), 3g compound antioxidant (being made of 1g antioxidant 1010 and 2g irgasfos 168).
Embodiment 7
3D printing material is prepared according to the method for embodiment 1, unlike, the composition of 3D printing composition in step (1)
Are as follows: 950g polyester-type thermoplastic polyurethane, 10g block copolymerization polypropylene, 10g propylene-octene elastomer, 23g propylene-octene are total
Polymers graft glycidyl methacrylate (POE-g-GMA), 2g titanium dioxide (average grain diameter is 1000 mesh), 2g silica
(average grain diameter is 1000 mesh), 3g compound antioxidant (being made of 1g antioxidant 1010 and 2g irgasfos 168).
Embodiment 8
3D printing material is prepared according to the method for embodiment 1, unlike, the group of the 3D printing composition in step (1)
Polyolefin in is polyethylene YG240F (being purchased from Yanshan Petrochemical company, melt mass flow rate 24g/10min).
Embodiment 9
3D printing material is prepared according to the method for embodiment 1, unlike, the group of the 3D printing composition in step (1)
Polyolefin in is that atactic copolymerized polypropene PP4925 (is purchased from Yanshan Petrochemical company, melt mass flow rate 25g/
10min)。
Embodiment 10
3D printing material is prepared according to the method for embodiment 1, unlike, the group of the 3D printing composition in step (1)
Polyolefin elastomer in is based elastomers 8200 (being purchased from E.I.Du Pont Company, shore hardness 30D).
Comparative example 1
3D printing material is prepared according to the method for embodiment 1, unlike, the group of the 3D printing composition in step (1)
Block copolymerization polypropylene is free of in.
Comparative example 2
3D printing material is prepared according to the method for embodiment 1, unlike, the group of the 3D printing composition in step (1)
Propylene-based elastomeric is free of in.
Comparative example 3
3D printing material is prepared according to the method for embodiment 1, unlike, the group of the 3D printing composition in step (1)
Block copolymerization polypropylene and propylene-based elastomeric are free of in.
Comparative example 4
3D printing material is prepared according to the method for embodiment 1, unlike, the composition of 3D printing composition in step (1)
Are as follows: 600g polyester-type thermoplastic polyurethane, 250g block copolymerization polypropylene, 100g propylene-octene elastomer, 43g propylene-octene
Copolymer grafted glycidyl methacrylate (POE-g-GMA), 2g titanium dioxide (average grain diameter is 1000 mesh), 2g titanium dioxide
Silicon (average grain diameter is 1000 mesh), 3g compound antioxidant (being made of 1g antioxidant 1010 and 2g irgasfos 168).
Comparative example 5
3D printing material is prepared according to the method for embodiment 1, unlike, the composition of 3D printing composition in step (1)
Are as follows: 600g polyester-type thermoplastic polyurethane, 100g block copolymerization polypropylene, 250g propylene-octene elastomer, 43g propylene-octene
Copolymer grafted glycidyl methacrylate (POE-g-GMA), 2g titanium dioxide (average grain diameter is 1000 mesh), 3g titanium dioxide
Silicon (average grain diameter is 1000 mesh), 3g compound antioxidant (being made of 1g antioxidant 1010 and 2g irgasfos 168).
Each composition weight accounting of above-described embodiment and the 3D printing composition of comparative example is listed in the table below in 1.
Table 1
Test case
3D printing material in embodiment and comparative example is detected as follows respectively:
1, elasticity performance test, test method are as follows: GB/T 2411-2008, the test result of shore hardness such as 2 institute of table
Show.
2, strength character is tested, and test method is as follows: GB/T 1040.2-2006, the test result of tensile strength such as table 2
It is shown.
3, toughness properties are tested, and test method is as follows: GB/T 1040.2-2006, the test result of break-draw strain is such as
Shown in table 2.
4, dimensional stability is tested, and test method is as follows: GB/T 17037.4-2003, the test result of molding shrinkage
As shown in table 2.
5, resistance to warping is tested, and test method is as follows: preparation 60mm × 30mm × 3mm cuboid exemplar, using vernier calliper
The amount of warpage of ruler measurement and the face of printer contacts baseplate, test result are as shown in table 2.
Table 2
It can be seen that macromolecule 3D printing composition of the invention by the result of table 2 with thermoplastic polyurethane, polyene
Hydrocarbon, polyolefin elastomer are primary raw material, and 3D printing material obtained has significant high resiliency, high-intensitive, high tenacity, high ruler
Very little stability and resistance to warping, have excellent performance and safety and environmental protection is nontoxic.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (13)
1. a kind of 3D printing composition, which is characterized in that the composition contains thermoplastic polyurethane, polyolefin, polyolefin elastic
Body, compatilizer, inorganic filler and antioxidant, on the basis of the total weight of the composition, the content of the thermoplastic polyurethane
Content for 50-95 weight %, the polyolefin is 1-20 weight %, the content of the polyolefin elastomer is 1-20 weight
Measure %, the content of the compatilizer is 1-20 weight %, the content of the inorganic filler is 0.1-2 weight %, described anti-oxidant
The content of agent is 0.05-1 weight %.
2. composition according to claim 1, wherein the thermoplastic polyurethane is polyester-type and/or polyether-type.
3. composition according to claim 1, wherein the polyolefin is atactic copolymerized polypropene, block copolymerization poly- third
At least one of alkene, homopolypropylene and polyethylene.
4. composition according to claim 1, wherein the polyolefin elastomer is based elastomers and/or propylene
Based elastomeric.
5. composition according to claim 1, wherein the compatilizer is the graft of polyolefin elastomer.
6. composition according to claim 1, wherein on the basis of the total weight of the composition, the thermoplastic poly ammonia
The content of ester is 70-90 weight %, the content of the polyolefin is 2-15 weight %, the content of the polyolefin elastomer is 2-
15 weight %, the compatilizer content be 2-10 weight %, the content of the inorganic filler is 0.2-1%, described anti-oxidant
The content of agent is 0.1-0.8 weight %；
It is further preferred that the content of the thermoplastic polyurethane is 77-86 weight on the basis of the total weight of the composition
Measure %, the content of the polyolefin is 5-10 weight %, the content of the polyolefin elastomer is 5-10 weight %, described compatible
The content of agent is 3-9 weight %, the content of the inorganic filler is 0.3-0.6%, the content of the antioxidant is 0.2-0.5
Weight %.
7. composition according to claim 6, wherein the average grain diameter of the inorganic filler is 500-5000 mesh, preferably
For 800-2000 mesh.
8. composition according to claim 7, wherein it is micro- that the inorganic filler is selected from silica, titanium dioxide, glass
In at least one of pearl, talcum powder, barium sulfate, montmorillonite and silicon powder, preferably silica, titanium dioxide and glass microballoon
At least one.
9. composition according to claim 6, wherein the antioxidant is four [β-(3,5- di-t-butyl -4- hydroxyls
Phenyl) propionic acid] pentaerythritol ester, three [2,4- di-tert-butyl-phenyl] phosphite esters and β-(3,5- di-t-butyl -4- hydroxy benzenes
At least one of base) propionic acid n-octadecyl alcohol ester.
10. a kind of preparation method of 3D printing material, which is characterized in that this method comprises: by claim 1-8 any one institute
The 3D printing composition stated successively is mixed, is granulated and formed.
11. according to the method described in claim 10, wherein, the temperature of the granulation is 190-240 DEG C, preferably 200-230
℃。
12. 3D printing material made from method described in 0 or 11 according to claim 1.
13. 3D printing material is in fusion sediment described in composition described in any one of claim 1-9 or claim 12
Application in method 3D printing.
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